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The province is in the Mekong valley. In dry season, from February to May, water in Mekong River declines, and allows islands to appear. Islands include Kaeng Tanglang at Si Sombun Village, close to Amphoe Chanuman, and Kaeng Hin Khan at Ban Hin Khan, 30 kilometres south of Amphoe Chanuman. The other two rivers in the province are the Lam Sae Bok and Lam Sae Bai.

Amnat Charoen gained city status during the reign of King Rama III. It was first administered from Nakhon Khemarat, and later from Ubon Ratchathani. It became a province in its own right on 12 January 1993, when it was split off from Ubon Ratchathani. It is thus one of the three newest provinces of Thailand, together with Nong Bua Lam Phu and Sa Kaeo.

The province is overwhelmingly agricultural. In 2008, Amnat Charoen locals developed the so-called "Dhamma agriculture" model based on self-governance and aimed at making the province a hub for organic farming. According to the Office of Agriculture Economics, Amnat Charoen in 2016 had a total of 883,499 rai planted in hom mali rice. Sugarcane plantations increased from 40,688 rai in 2015 to 51,446 rai in 2016.[3]

In the middle of the provincial seal is an image of the Buddha called Phra Mongkol Ming Muang. Also known as Phra Yai (Big Buddha), this 20 m high statue is among the most sacred in the city of Amnat Charoen.[2]